CN101748650B - Preparation and application method for fly ash fiber and wood fiber mixed dissolving modifier - Google Patents
Preparation and application method for fly ash fiber and wood fiber mixed dissolving modifier Download PDFInfo
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- CN101748650B CN101748650B CN2009102013221A CN200910201322A CN101748650B CN 101748650 B CN101748650 B CN 101748650B CN 2009102013221 A CN2009102013221 A CN 2009102013221A CN 200910201322 A CN200910201322 A CN 200910201322A CN 101748650 B CN101748650 B CN 101748650B
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Abstract
The invention discloses a preparation and application method for a fly ash fiber and wood fiber mixed dissolving modifier, which is characterized by comprising the following steps: firstly, polymerizing acrylic acid to obtain aqueous solution of polyacrylic acid, adding N,N-dimethyl-1,3-propane diamine into the solution to perform amidation, heating a product after the amidation to between 50 and 70 DEG C, then adding chloroactic acid into the solution, and finally adding NaOH into the solution to neutralize the solution so as to obtain an amphoteric polyacrylic acid amide modifier; and secondly, dispersing 3 to 5 percent fly ash fiber by weight of dry fiber into water, soaking the fly ash fiber for 20 to 30 minutes, adding the amphoteric polyacrylic acid amide modifier which is diluted one time by using water into the solution, stirring the solution for 3 to 5 minutes, then stopping stirring, uniformly adsorbing the fly ash fiber for 20 to 40 minutes, and taking the fly ash fiber out of the water phase to obtain modified fly ash fiber. The modified fly ash fiber can be directly mixed with wood pulp or straw pulp to make paper, or the modified fly ash fiber can be dried and then is mixed with wood pulp or straw pulp in the aqueous solution to make paper. The amphoteric polyacrylic acid amide modifier prepared by the method can enhance the binding force between the fly ash fiber and the wood pulp fiber or the straw pulp fiber, and improve the strength of paper doped with the fly ash fiber.
Description
Technical field
The present invention relates to the preparation and the application process of a kind of coal ash fiber and xylon mixed dissolving modifier, specifically, is a kind of preparation and technique for applying method that is used for the coal ash fiber and the xylon mixed dissolving modifier of papermaking.
Background technology
Wood pulp fibre or straw pulp fiber are a kind of fascicular textures, each bundle is by a lot of more tiny fibrous, pass through making beating in the paper-making process, the fabric thrashing of pencil is become tiny fiber, tiny fiber surface has a large amount of hydrophilic hydroxyls, these hydroxyls can make fiber can better disperse in water, also make between the fiber and can mutually combine by hydrogen bond.Coal ash fiber is to add flux with flyash to become fine under high-temperature fusion, and the coal ash fiber structure is single, and the surface is more smooth, can not be dispersed as thinner fiber, and the hydroxy radical content of surface of fly ash fiber also lacks a lot than wood pulp fibre or straw pulp fiber.It is poor that this just causes coal ash fiber to reach the interfibrous adhesion of coal ash fiber and wood pulp fibre or straw pulp to each other, and the adhesion that how to improve coal ash fiber has become coal ash fiber to be applied to the papermaking key of success.
Chinese patent CN101503280 discloses a kind of inorfil softening intensifier and preparation method thereof, with H
2O
2, polyvinyl alcohol and potassium hydroxide is at 50 ℃～60 ℃ reaction 2～4h, reaction finishes the back and adds etherifying agent, at 50 ℃～70 ℃ reaction 4～8h down, regulator solution pH=7～8 obtain inorfil softening intensifier.The softening intensifier of this invention is applicable to the various inorganic fibers of producing by physics or hot melt, comprises that the softening intensifier of basalt fibre, wollastonite fibre, sepiolite fibre, gypsum fiber, coal ash fiber and glass fibre is handled.Can improve the flexibility and the intensity of inorfil by this softening intensifier, improve the drawback that inorfil is easy to rupture at making beating, dispersion, course of conveying, change the electric charge on inorfil surface, strengthen the adhesion of inorfil and string, greatly improve inorfil and be used for the application performance that wet papermaking is made paper, heat-preservation cotton plate etc.
Chinese patent CN1843992 discloses a kind of wind cooling method and device thereof of preparing fiber by fly ash.Technical scheme is: its method is, end at the main shaft that connects the fine roller of system feeds compressed air, compressed air is worn the hole of penetrating the fine roller front end of system, and the part heat of taking away on the fine roller of system makes its cooling, makes the fine roller of system reduce to suitable temperature by regulating compressed-air actuated pressure and throughput.Its device comprises the fine roller of system, main shaft, rolling bearing, blast pipe, airduct and air compressor machine, rear end and main shaft one end of making fine roller are tightly connected, housing washer is fixed on main shaft the other end, and the blast pipe close-fitting is at rolling bearing inner ring, and airduct one end connects blast pipe one end and connects air compressor machine.Its advantage is: can produce diameter less than 5 μ m coal ash fibers, its slag-containing rate amount is lower than below 5%; The fiber that is obtained is thinner, and is better to the separating effect of slag ball; Can satisfy the technological requirement of heterogeneity powdered coal ash system fibre, also guarantee the service life of roller head simultaneously, can reach about 200 hours usually.
Chinese patent CN1834047 discloses a kind of fiber deslagging method of coal ash.Its technical scheme comprises the following steps: that raw material crushing is loose; Make fibre stuff; Slurry flows and makes slag ball and fiber separation; Fiber collection.Its advantage is: 1) adopt the content of its slag ball of coal ash fiber that the inventive method obtained extremely low, slag ball rate is lower than 0.2%, and the fiber fineness height can be isolated the coal ash fiber of the at different levels fineness of fineness below 5 μ m; 2) the inventive method can not produce any environmental pollution, and institute's water can use repeatedly in producing, and saves the water source; 3) coal ash fiber that utilizes the inventive method and obtained can replace string to be used for papermaking or produce various composites, thereby can save a large amount of timber and string, can avoid or reduce simultaneously the environmental pollution that is caused when making string.
Though the content that above-mentioned various invention relates to helps coal ash fiber and is applied to papermaking, be beyond one's ability to the improvement of the bonding state of coal ash fiber and string.Therefore, the present invention is starting point as improving target from the surface chemistry performance of improving coal ash fiber, increases the adhesion of coal ash fiber and string by adding surfactant.The innovative approach that the present invention addresses this problem is:: on the polyacrylic chain of water-soluble polymer, connect CATION and anionic group, on the water-soluble polymer polyacrylic acid strand a lot of carboxyls are arranged, the ability that good hydrophily and formation hydrogen bond are arranged, the cation group that connects on the polyacrylic acid strand easily and on wood pulp or the straw pulp fiber with the negative electrical charge effect, and receive on wood pulp or the straw pulp fiber, reach to each other and wood pulp or straw pulp fiber combining power thereby improve coal ash fiber.The anionic group that connects on the polyacrylic acid strand helps to make the polyacrylic acid strand to stretch, and makes the polyacrylic acid molecule spread over the surface of coal ash fiber equably.
Summary of the invention
The preparation of a kind of coal ash fiber and xylon mixed dissolving modifier and application process, it is characterized in that: at first with acroleic acid polymerization, obtain the polyacrylic acid aqueous solution, again toward wherein adding N, N-dimethyl-1, the 3-propane diamine carries out amidatioon, product after the amidatioon is warming up to 50～70 ℃, add monoxone then, add NaOH at last and neutralize, obtain the both sexes polyacrylic acid amide modifier.Secondly, coal ash fiber is dispersed in the water, in the dry pulp weight concentration is 3～5%, soaked 20～30 minutes, and added the both sexes polyacrylic acid amide modifier of 1 times of dilute with water, stirred 3～5 minutes, stop to stir, equilibrium adsorption 20～40 minutes is taken out coal ash fiber from aqueous phase, obtain the coal ash fiber after the modification.Coal ash fiber after the modification can be directly and wood pulp or straw pulp copy paper, copy paper with wood pulp or straw pulp again after also can being dried.
Described acroleic acid polymerization method is: add entry and sodium pyrosulfite earlier in reactor, the addition of sodium pyrosulfite is 1～3% of an acrylic acid oven dry weight, reactor is warming up to 90 ℃, then the acrylic acid aqueous solution of concentration 30～70% and the ammonium persulfate aqueous solution of concentration 5～10% is added drop-wise in the reactor simultaneously.The ammonium persulfate addition is: the oven dry weight of ammonium persulfate is 0.5～1.5% of an acrylic acid oven dry weight, and the dropping time is 2～5 hours, is warming up to 95～98 ℃ then, is incubated 0.5～1 hour, is cooled to below 50 ℃.
Described N, N-dimethyl-1, the addition of 3-propane diamine is 10～30% of an acrylic acid oven dry weight.
Described chloroacetic addition is: monoxone and N, and N-dimethyl-1, the mol ratio of 3-propane diamine is 1: 1.
The addition of described NaOH is: NaOH and chloroacetic mol ratio are 1: 1.
Described at coal ash fiber aqueous phase adding both sexes polyacrylic acid amide modifier, its addition is: both sexes polyacrylic acid amide modifier oven dry weight is 1～5% of a coal ash fiber oven dry weight.
Described modified coal ash fiber and wood pulp or straw pulp mixed with fibers, in dry pulp modified coal ash fiber: wood pulp or straw pulp fiber are 1: 2～5.
Both sexes polyacrylic acid amide modifier with this method preparation can improve the dispersiveness of coal ash fiber in water, can increase the adhesion between coal ash fiber and wood pulp or the straw pulp fiber, improves to be mixed with the coal ash fiber strength of paper.
The specific embodiment
Embodiment 1
In the reactor that 100 liters of bands stir, heat, add 20kg water, open and stir, the sodium pyrosulfite of 0.5kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the acrylic acid aqueous solution 40kg of concentration 50% and the ammonium persulfate aqueous solution 3kg of concentration 10% are added drop-wise in the reactor simultaneously.The dropping time is 4 hours, is warming up to 95 ℃ then, is incubated 0.5 hour, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propane diamine 4kg is warming up to 70 ℃ with reactor, adds monoxone 3.7kg then, adds NaOH 1.6kg at last and neutralizes, and obtains weight concentration and be 41.4% both sexes polyacrylic acid amide modifier 68kg.
The 800kg coal ash fiber is dispersed in 20 tons of water, soaked 30 minutes, taking by weighing above-mentioned both sexes polyacrylic acid amide modifier 68kg adding 68kg water dilutes, join in the reactor, stirred 5 minutes, stop to stir, equilibrium adsorption 20 minutes, coal ash fiber is taken out from water, obtain the coal ash fiber after the modification, the coal ash fiber after the modification is directly used in wood pulp or straw pulp is copied paper.Modified coal ash fiber and wood pulp or straw pulp mixed with fibers, in dry pulp modified coal ash fiber: wood pulp or straw pulp fiber are 1: 2.
Embodiment 2
In the reactor that 100 liters of bands stir, heat, add 20kg water, open and stir, the sodium pyrosulfite of 0.4kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the acrylic acid aqueous solution 20kg of concentration 70% and the ammonium persulfate aqueous solution 4.2kg of concentration 5% are added drop-wise in the reactor simultaneously.The dropping time is 5 hours, is warming up to 98 ℃ then, is incubated 1 hour, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propane diamine 1.9kg, reactor is warming up to 50 ℃, add monoxone 1.7kg then, add NaOH 0.7kg at last and neutralize, obtain weight concentration and be 40.0% both sexes polyacrylic acid amide modifier 45kg.
The 360kg coal ash fiber is dispersed in 12 tons of water, soaked 20 minutes, taking by weighing above-mentioned both sexes polyacrylic acid amide modifier 45kg adding 45kg water dilutes, join in the reactor, stirred 3 minutes, and stopped to stir equilibrium adsorption 40 minutes, coal ash fiber is taken out from water, dries, obtain the coal ash fiber after the modification.Modified coal ash fiber and wood pulp or straw pulp mixed with fibers, in dry pulp modified coal ash fiber: wood pulp or straw pulp fiber are 1: 5.
Embodiment 3
In the reactor that 100 liters of bands stir, heat, add 15kg water, open and stir, the sodium pyrosulfite of 0.15kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the acrylic acid aqueous solution 50kg of concentration 30% and the ammonium persulfate aqueous solution 1.5kg of concentration 5% are added drop-wise in the reactor simultaneously.The dropping time is 5 hours, is warming up to 97 ℃ then, is incubated 40 minutes, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propane diamine 1.5kg, reactor is warming up to 60 ℃, add monoxone 1.4kg then, add NaOH 0.6kg at last and neutralize, obtain weight concentration and be 28.1% both sexes polyacrylic acid amide modifier 64kg.
The 420kg coal ash fiber is dispersed in 14 tons of water, soaked 25 minutes, taking by weighing above-mentioned both sexes polyacrylic acid amide modifier 64kg adding 6410kg water dilutes, join in the reactor, stirred 4 minutes, and stopped to stir equilibrium adsorption 30 minutes, coal ash fiber is taken out from water, dries, obtain the coal ash fiber after the modification.Modified coal ash fiber and wood pulp or straw pulp mixed with fibers, in dry pulp modified coal ash fiber: wood pulp or straw pulp fiber are 1: 3.5.
Embodiment 4
In the reactor that 100 liters of bands stir, heat, add 40kg water, open and stir, the sodium pyrosulfite of 0.24kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the acrylic acid aqueous solution 20kg of concentration 40% and the ammonium persulfate aqueous solution 1.7kg of concentration 7% are added drop-wise in the reactor simultaneously.The dropping time is 3.5 hours, is warming up to 96 ℃ then, is incubated 45 minutes, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propane diamine 2.4kg, reactor is warming up to 65 ℃, add monoxone 2.2kg then, add NaOH 0.9kg at last and neutralize, obtain weight concentration and be 21.8% both sexes polyacrylic acid amide modifier 58kg.
The 1200kg coal ash fiber is dispersed in 24 tons of water, soaked 30 minutes, taking by weighing above-mentioned both sexes polyacrylic acid amide modifier 58kg adding 58kg water dilutes, join in the reactor, stirred 5 minutes, stop to stir, equilibrium adsorption 25 minutes, coal ash fiber is taken out from water, obtain the coal ash fiber after the modification, direct wood pulp of the coal ash fiber after the modification or straw pulp are copied paper.Modified coal ash fiber and wood pulp or straw pulp mixed with fibers, in dry pulp modified coal ash fiber: wood pulp or straw pulp fiber are 1: 4.
Embodiment 5
In the reactor that 100 liters of bands stir, heat, add 25kg water, open and stir, the sodium pyrosulfite of 0.3kg is joined in the reactor, it is fully dissolved, open heating and make reactor be warmed up to 90 ℃, then the acrylic acid aqueous solution 25kg of concentration 60% and the ammonium persulfate aqueous solution 1.8kg of concentration 8% are added drop-wise in the reactor simultaneously.The dropping time is 4.5 hours, is warming up to 98 ℃ then, is incubated 0.5 hour, is cooled to below 50 ℃.In reactor, add N again, N-dimethyl-1,3-propane diamine 3.7kg, reactor is warming up to 70 ℃, add monoxone 3.4kg then, add NaOH 1.6kg at last and neutralize, obtain weight concentration and be 39.5% both sexes polyacrylic acid amide modifier 56kg.
The 1100kg coal ash fiber is dispersed in 27 tons of water, soaked 28 minutes, taking by weighing above-mentioned both sexes polyacrylic acid amide modifier 56kg adding 56kg water dilutes, join in the reactor, stirred 3 minutes, stop to stir, equilibrium adsorption 35 minutes, coal ash fiber is taken out from water, obtain the coal ash fiber after the modification, direct wood pulp of the coal ash fiber after the modification or straw pulp are copied paper.Modified coal ash fiber and wood pulp or straw pulp mixed with fibers, in dry pulp modified coal ash fiber: wood pulp or straw pulp fiber are 1: 4.5.
Claims (6)
1. the preparation method of a coal ash fiber modifier, it is characterized in that: at first with acroleic acid polymerization, obtain the polyacrylic acid aqueous solution, again toward wherein adding N, N-dimethyl-1, the 3-propane diamine carries out amidatioon, product after the amidatioon is warming up to 50～70 ℃, add monoxone then, add NaOH at last and neutralize, obtain the both sexes polyacrylic acid amide modifier; Secondly, coal ash fiber is dispersed in the water, in dried fibre weight concentration is 3～5%, soaks 20～30 minutes, adds the both sexes polyacrylic acid amide modifier of 1 times of dilute with water, stirred 3～5 minutes, stop to stir, equilibrium adsorption 20～40 minutes is taken out coal ash fiber from aqueous phase, obtain the coal ash fiber after the modification, the coal ash fiber after the modification can be copied paper with wood pulp or straw pulp mixed with fibers;
Described acroleic acid polymerization method is: add entry and sodium pyrosulfite earlier in reactor, the addition of sodium pyrosulfite is 1～3% of an acrylic acid oven dry weight, reactor is warming up to 90 ℃, be added drop-wise to the acrylic acid aqueous solution of concentration 30～70% and the ammonium persulfate aqueous solution of concentration 5～10% in the reactor simultaneously then, wherein the ammonium persulfate addition is: the oven dry weight of ammonium persulfate is 0.5～1.5% of an acrylic acid oven dry weight, the dropping time is 2～5 hours, be warming up to 95～98 ℃ then, be incubated 0.5～1 hour, be cooled to below 50 ℃.
2. the described method of claim 1, N wherein, N-dimethyl-1, the addition of 3-propane diamine is 10～30% of an acrylic acid oven dry weight.
3. the described method of claim 1, wherein chloroacetic addition is: monoxone and N, N-dimethyl-1, the mol ratio of 3-propane diamine is 1: 1.
4. the described method of claim 1, wherein the addition of NaOH is: NaOH and chloroacetic mol ratio are 1: 1.
5. the described method of claim 1, wherein the addition of both sexes polyacrylic acid amide modifier is: both sexes polyacrylic acid amide modifier oven dry weight is 1～5% of a coal ash fiber oven dry weight.
6. the described method of claim 1, wherein modified coal ash fiber and wood pulp or straw pulp mixed with fibers, in dry pulp modified coal ash fiber: wood pulp or straw pulp fiber are 1: 2～5.
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| CN103739776A (en) * | 2014-01-02 | 2014-04-23 | 华东理工大学 | Amphiprotic polyhydroxyl polymer for inorganic superfine fiber papermaking and preparation method thereof |
| CN104313942B (en) * | 2014-10-09 | 2017-04-12 | 济源市金港特纤科技有限公司 | Synthesis method for inorganic fiber softener |
| CN105199166A (en) * | 2015-09-29 | 2015-12-30 | 安徽蓝德集团股份有限公司 | Flame-retardant computer cable sheath material with excellent mechanical properties |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580391A (en) * | 2004-05-18 | 2005-02-16 | 华东理工大学 | Flyash fiber pulp and papermaking method using same as raw material |
| US20050257887A1 (en) * | 2004-05-24 | 2005-11-24 | Tsotsis Thomas K | Method and apparatus for melt-bonded materials for tackification of dry fabric preforms |
| CN1843992A (en) * | 2006-04-03 | 2006-10-11 | 彭苏宁 | Wind cooling method for preparing fiber by fly ash and apparatus thereof |
| CN101250032A (en) * | 2008-03-24 | 2008-08-27 | 华东理工大学 | Technology for coal ash fibre surface treatment and use of asphalt reinforcing modification thereof |
| CN101503280A (en) * | 2009-03-06 | 2009-08-12 | 陕西科技大学 | Inorfil softening intensifier and preparation thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580391A (en) * | 2004-05-18 | 2005-02-16 | 华东理工大学 | Flyash fiber pulp and papermaking method using same as raw material |
| US20050257887A1 (en) * | 2004-05-24 | 2005-11-24 | Tsotsis Thomas K | Method and apparatus for melt-bonded materials for tackification of dry fabric preforms |
| CN1843992A (en) * | 2006-04-03 | 2006-10-11 | 彭苏宁 | Wind cooling method for preparing fiber by fly ash and apparatus thereof |
| CN101250032A (en) * | 2008-03-24 | 2008-08-27 | 华东理工大学 | Technology for coal ash fibre surface treatment and use of asphalt reinforcing modification thereof |
| CN101503280A (en) * | 2009-03-06 | 2009-08-12 | 陕西科技大学 | Inorfil softening intensifier and preparation thereof |
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